EP0238078B1 - Verfahren zur Herstellung von Polysilazanen und Silicium-Nitriden - Google Patents

Verfahren zur Herstellung von Polysilazanen und Silicium-Nitriden Download PDF

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EP0238078B1
EP0238078B1 EP87104014A EP87104014A EP0238078B1 EP 0238078 B1 EP0238078 B1 EP 0238078B1 EP 87104014 A EP87104014 A EP 87104014A EP 87104014 A EP87104014 A EP 87104014A EP 0238078 B1 EP0238078 B1 EP 0238078B1
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sub
reaction
acid
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amine
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EP0238078A2 (de
EP0238078A3 (en
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Roswell Easton King Iii
Bernard Kanner
Steven Philip Hopper
Curtis Louis Jr. Schilling
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage

Definitions

  • This invention generally relates to a liquid phase process for making polysilazanes substantially free of halide impurities via the transamination and condensation of certain aminosilanes, particularly tris-dimethylaminosilane and/or vinyl-tris (dimethylamino)silane, with ammonia and/or monomethylamine in the presence of a Bronsted acid catalyst.
  • the resulting polysilazane polymers range from fluids and resins to insoluble powders. These silazane polymers can be used as precursors for silicon based ceramic materials, binders or fibers.
  • Silicon nitride, Si3N4, is currently a material of great potential and interest in that its ceramic properties include high temperature stability, chemical inertness, oxidation resistance and extreme hardness.
  • silicon nitride has been prepared by a variety of methods, including the reaction of silicon metal with gaseous N2 and/or NH3, giving reaction-bonded silicon nitride, ("RBSN").
  • RBSN is useful for forming bulk parts via methods of powder metallurgy; for example hot pressing, sintering, casting or extruding.
  • Another method of preparing silicon nitride is via chemical vapor deposition ("CVD").
  • CVD chemical vapor deposition
  • the purity of the product is related to the purity of the reactant gases.
  • the CVD method is a fundamental process for fabricating electronic materials and devices which require high purity silicon nitride.
  • these silazane polymers are synthesized from the reaction of halogen containing silanes with ammonia [J. Am. Ceramic. Soc. 67 132 (1984)], or by the reaction of halogen containing alkylsilanes with ammonia [J. Poly. Sci. A2 3179-3189 (1964)], primary amines [Acta. Chem. Scand. 13 29-34 (1959)], diamines [J. Poly. Sci. A2 44-55 (1964)] or silazanes.
  • Still another object of the invention is to allow the transamination byproduct, e.g., dimethylamine, to be recycled into the process for preparing dimethylaminosilanes.
  • the transamination byproduct e.g., dimethylamine
  • Yet another object of this invention is to provide silazane polymers made by the process of the invention.
  • this invention relates to a novel process for making polysilazanes which can be used as precursors for silicon nitride containing ceramic powders, composites, binders and fibers.
  • This process is economically attractive in that it eliminates a process step for removing halide impurities found in the production of prior art polysilazanes.
  • this invention provides the transamination and condensation of certain aminosilanes with ammonia or other useful amines to form hydrosilazane and silazane polymers free of halogen impurities.
  • the invention provides tris(dimethylamino) silane as starting materials which can be transaminated with ammonia or other useful amines and condensed entirely in one liquid phase and in one vessel to provide polysilazane products. Because these starting aminosilanes are halogen free, substantially no hydrohalogen impurities result. Thus, the difficult and often imperfect solid/solid or liquid/solid phase separation step in which these impurities are filtered or calcined out of the silazane polymer is eliminated.
  • the silazane polymer unit is subsequently condensed to form the actual polymer as is well known to those skilled in the art. Additionally, all the silazane polymers have three or more repeating units. It should be noted that the (CH3)2NH byproduct generated from the reaction can be recycled to further prepare starting aminosilanes.
  • the starting aminosilanes used in the present invention are prepared by the direct reaction of dimethylamine with silicon metal as is taught in U.S. - A - 4,255,348.
  • the present invention is able to provide polysilazanes essentially free of amine hydrohalogen impurities.
  • the aminosilane starting reactant of the general reaction can be divided into two classes: Class 1 - aminosilanes bearing Si-H linkages Class 2 - aminosilanes that do not contain Si-H linkage. This distinction is made between the two classes because, as discussed below, a wider variety of catalysts are effective in the transamination and condensation of Class 1 compounds.
  • the members of Class 1 can be any alkylaminosilane such as Me(Me2N)2SiH or Et(Me2N)2SiH or dihydrodiaminosilanes such as (Me2N)2SiH2.
  • the preferred member of Class 1 is tris(dimethylamino)silane.
  • Me is methyl and Et is ethyl.
  • the amines of the invention are the amines having a molecular weight of less than 45, such as ammonia, and/or methyl amine in terms of obtaining the highest weight percent ceramic yields.
  • the starting aminosilanes of the invention can be efficiently displaced, through Bronsted acid catalysis, with the amines mentioned above.
  • the prior art teaches the displacement of lower molecular weight amines by higher molecular weight amines rather than the opposite. This is apparently because of the difficulties involved in displacing a higher molecular weight amine group, which has a higher boiling point with a lower molecular weight amine, which, because of its lower boiling point, normally evaporates first. As noted, it has been advantageously found that with the starting reactants used in this invention, displacement of the higher molecular weight amines with lower molecular weight amines is readily feasible.
  • the lower molecular weight amine groups present in the silazane polymers are advantageous because, having little or no carbon content in the silazane polymer, a greater overall weight percent yield of Si3N4 following pyrolysis is provided. Carbon-containing substituents are lost during high temperature pyrolysis and correspondingly reduce the weight percent yield of the silicon nitride ceramic; low carbon content polymers thus result in higher yields.
  • the ratio of starting aminosilane to the transaminating amine is not critical to the practice of the invention.
  • a preferred ratio is from 0.01:1 to 2.0:1 molar amounts of starting aminosilane reactant relative to the transaminating amine reactant.
  • the acid catalysts used in this reaction depend on whether the starting aminosilane is characterized into Class 1 or Class 2 as defined above.
  • the silicon substrate contains an Si-H linkage, i.e. Class 1, the transamination and subsequent condensation reactions are unexpectedly catalyzed by sources of carbon dioxide.
  • the transamination of Class 1 aminosilane compounds is also effectively catalyzed by relatively mild acidic reagents such as carboxylic acids, e.g., acetic acid.
  • acidic reagents such as carboxylic acids, e.g., acetic acid.
  • the transamination of Class 1 aminosilanes is most efficiently catalysed by the same strong organic or inorganic acid catalysts as discussed below for Class 2 aminosilane compounds.
  • Class 2 aminosilane compounds are relatively unaffected by the mild organic acids mentioned above or "sources of CO2" type catalysis. These Class 2 aminosilanes which do not contain silicon-bonded hydrogen are more effectively transaminated using strong organic or inorganic acids. These more effective strong acid catalysts are characterized by pKa values relative to water of less than 2.2.
  • Representative strong organic acids are the sulfonic acids, e.g., methane sulfonic acid, para-toluene sulfonic acid, or trifluoromethane sulfonic acid. Trifluoroacetic acid is an example of a relatively strong carboxylic acid.
  • strong inorganic acids include sulfuric acid, nitric acid or phosphoric acid.
  • the loadings are in the range of 0.5-30 mol percent based on starting aminosilane, preferably 1-10 mol percent.
  • the loadings are in the range of 0.01-10 mol percent based on starting aminosilane, preferably 0.1-5 mol percent.
  • the transamination reactions of the present invention can be conveniently run in the presence of appropriate solvents with the stipulation that the solvents should be largely unreactive with the aminosilane, the incoming amine and the transamination catalyst of the reaction under typical reaction conditions and should allow for reasonable reaction rates.
  • the solvent is selected from alkanes and alkylated benzenes having 6 - 20 carbon atoms wherein the reaction products are insoluble or alkanes and alkylated benzenes having 6 - 10 carbon atoms wherein the reaction products are soluble.
  • Typical solvents are alkanes such as heptanes, octanes, or decane and alkylated benzenes such as toluene, xylene or mesitylene. Sufficient solvent is used so that the reaction may adequately take place in a liquid environment. The amount of solvent, however, is not critical to the reaction. The preferred ratio of starting reactant to solvent is from 0.1:1.0 to 10:1, preferably 1:1 by either weight or volume.
  • the solvent may be removed by heat and vacuum evaporation without a filtration step if the resulting polysilazane is a solvent soluble product, or by filtration if the resulting polysilazane is a solvent insoluble product.
  • This filtration step is straightforward and expedient in the sense that it simply separates the insoluble product from the unreactive solvent. This differs from a filtration to remove by-products, such as ammonium hydrogen halide salts, in that it does not require an additional process step, i.e., solvent removal by evaporation to isolate the product. Thus, this process step is avoided when using aminosilanes instead of halogen containing silanes.
  • Another aspect of the invention is that, because no calcination or filtration step is needed to eliminate halogen impurities, the entire reaction can, but need not, take place in one vessel and in a liquid phase. This results in greatly improved economics in the preparation of the polysilazane.
  • the degree of polymerization of the silazanes depends to some degree on the temperature of the reaction.
  • the polysilazanes produced via transamination and subsequent condensation reactions at ambient temperature will be of significantly lower molecular weight than those prepared at higher temperatures.
  • These low molecular weight polisilizanes may be beneficial for applications requiring such low weight. Consequently, the reaction temperature can be used to impart useful properties to the polysilazanes with respect to their molecular weights depending on the desired application.
  • the transamination and subsequent condensation reactions can be performed efficiently in the temperature range of 20° to 200°C in a largely unreactive solvent. Within this wide range are preferred ranges that vary based on starting reactants and the overall product morphology desired.
  • a precursor for high purity Si3N4 the reaction of (Me2N)3SiH with NH3 in the presence of a strongly acidic transamination catalyst, such as H2SO4, is preferably performed in the temperature range of 100° to 200°C.
  • H2SO4 strongly acidic transamination catalyst
  • silazane polymer which may be used as an impregnant in a porous pre-formed ceramic part. It would therefore be useful to prepare a silazane polymer which is a liquid which may also have the added feature of being soluble in an unreactive solvent.
  • a likely candidate for the preparation of such a silazane polymer would be derived from the reaction of (Me2N)3SiH with MeNH2 in the presence of a mildly acidic transamination catalyst, e.g., para-toluene sulfonic acid, preferably preformed in the temperature range of 20° to 80°C.
  • silazane polymer which is resinous and can be formed into shapes or pulled into fibers.
  • This silazane polymer would be required to have a significant degree of crosslinking to increase its viscosity. This necessitates performing the reaction at higher temperatures in the presence of a strong acid catalyst.
  • the transamination reaction can be effectiely performed under a variety of temperature ranges which are largely dictated by the starting reactants, the transamination catalyst, and the desired product morphology and therefore cannot be limited to any particular temperature range, in general.
  • the starting aminosilane reactant, transaminating reactant and catalyst can generally be combined in any order, they are preferably combined in the following way, i.e. solvent, starting aminosilane reactant, catalyst and then transaminating amine reactant.
  • the reaction may take anywhere from 1 to 24 hours for transamination and subsequent condensation polymerization to occur.
  • soluble ceramic precursors were characterized by conventional analytical techniques such as FTIR and 1H, 13C, and 29Si NMR spectroscopy. Insoluble ceramic precursors were identified by FTIR spectroscopy (see Smith, A. L., Analysis of Silicones, Wiley, 1974).
  • a 1-liter 3 neck round bottom flask with standard taper joints was fitted with a Friedrich condenser, thermometer, heating mantle, magnetic stirrer and gas sparging tube, plus valves for maintaining a dry nitrogen atmosphere coupled with a pressure release bubbler.
  • the aminosilane 200 g ; 1.24 mol
  • Ammonia was sparged through the mixture for 15 m and then the carbamate salt (Me2NH2)+(CO2NMe2) ⁇ (16.6 g ; 1.24 mol) was added.
  • the reaction mixture was heated with NH3 sparging and stirring to the reflux temperature 115°C for 8 hours while monitoring the reaction via GLC (gas-liquid-chromatographie) for loss of starting aminosilane HSi(NMe2)3.
  • the material inside the flask appeared to be a water white liquid during the entire length of the reaction.
  • the reaction was determined to be complete and flask was cooled and refitted with two stoppers and a by vacuum evaporation (0.133 mbar - 0.1 mm Hg) and heating 80-100°C to yield a white glassy solid.
  • the glassy solid was washed with 100 ml of pentane and the pentane washings were discarded.
  • the white material was transferred under N2 to a 500 ml 1 neck round bottom flask and further dried under vacuum for 6 hours (0.0133 mbar - 0.01 mm Hg).
  • the yield of the white free flowing glassy material was 92.9 g .
  • the white solid was pyrolyzed to 1000°C under a N2 purge at atmospheric pressure to give a Si3N4 composition with a yield of 65.4% based on g material charged (5.03 g ) vs g material obtained (3.29 g ).
  • Example 2 In an apparatus as described in Example 1 using a 2 liter flask instead, were combined toluene (375 ml) and HSi(NMe2)3 (369.9 g ; 2.2932 mol) via a cannulating device. The mixture was sparged with MeNH2 for 15 min and then charged with the carbamate salt (Me2NH2)+(CO2NMe2) ⁇ (30.73 g ; 2.2932 mol). The reaction mixture was heated with MeNH2 sparging and stirring to the reflux temp of 115°C for 9 hours while monitoring the reactor via GLC for the loss of the starting aminosilane reactant during the entire length of the reaction.
  • Me2NH2 carbamate salt
  • a 1 liter 3 neck round bottom flask was fitted with a Friedrich condenser, heating mantle, magnetic stirrer, thermometer and fittings for a dry N2 atmosphere and a pressure release bubbler.
  • the apparatus was evacuated and refilled with N2 before the toluene (300 ml), HSi(NMe2)3 (199.1g; 1.234 mol) and allyl amine (211.4 g ; 3.703 mol) were charged into the flask via a cannulating device. After stirring for 30 min without heating, the carbamate salt (Me2NH2)+(CO2NMe2) ⁇ (16.54 g ; 1.234 mol) was added. Immediate gas evolution was observed.
  • the reaction mixture was heated for 4 hours at a reflux temperature of 110°C while monitoring the reaction via GLC for the starting silane HSi(NMe2)3. After 4 hours the reaction was determined to be complete and the flask was cooled and refitted with two stoppers and vacuum adapter with stopcock. The contents of the flask appeared to be a water white liquid during the entire length of the reaction. The toluene solvent and excess allylamine were removed by vacuum evaporation (0.133 mbar - 0.1 mm Hg) and heating to 80°C.
  • the colorless liquid was pyrolyzed to 1000°C under a N2 purge at atmospheric pressure to give a Si3N4 composition with a yield of 40.0% based on material charged (5.33 g ) vs. material obtained (2.12 g ).
  • Example 2 An apparatus as described in Example 2 was vacuum evacuated and refilled with N2 before toluene (400 ml), aniline (381.9 g , 4.10 mol), and HSi(NMe2)3 (220.48 g ; 1.3669 mol) were charged via a cannulating device. The mixture was stirred at 20°C for 30 min and the carbamate salt (Me2NH2)+(CO2NMe2) ⁇ (1.29 g ; 9.61 x 10 ⁇ 3 mol) was then added. As the reaction was brought to the reflux temperature of 117°C, vigorous gas evolution was observed. The mixture was heated at the reflux temperature for 3 hours until no further gas evolution was observed.
  • carbamate salt Me2NH2NH2+(CO2NMe2) ⁇ (1.29 g ; 9.61 x 10 ⁇ 3 mol
  • the flask was cooled to room temperature and the contents inside the flask changed from a water white solution to a crystalline slurry.
  • the apparatus was refitted with two glass stoppers and a vacuum adapter with stopcock.
  • the toluene and excess aniline were removed by vacuum evaporation (0.133 mbar - 0.1 mm Hg) and heating to 120°C.
  • the resultant solid material was washed liberally with pentane, filtered and dried under vacuum to give a final yield of 328.3 g of white crystalline needles.
  • a 200 ml 1 neck round bottom flask was fitted with a coiled condenser, magnetic stirrer, heating mantle and fittings for maintaining a dry N2 atmosphere and a pressure release bubbler.
  • the apparatus was vacuum evacuated and refilled with N2 before toluene (40 ml), aniline (27.05 g ; 02905 mol) and HSi(NMe2)3 (15.62 g ; .0968 mol) were charged via syringe.
  • the mixture was stirred for 15 min at 20°C before adding the carbamate salt (Me2NH2)+(CO2NMe2) ⁇ (0.129 g , 9.61x10 ⁇ 4 mol).
  • a 500 ml 3 neck round bottom flask was fitted with a reflux condenser, magnetic stirrer, gas sparging tube and a nitrogen adapter with a pressure release bubbler.
  • the flask was charged with toluene (150 ml) and HSi(NMe2)3 (98.6 g , 0.611 mol) via syringe and the water white solution was sparged with NH3 for 15 minutes.
  • CF3SO3H (0.54 ml) via syringe the solution become cloudy.
  • 1 hour of NH3 sparging at room temperature the contents of the flask had transformed to a white slurry.
  • the aminosilane, HSi(NMe2)3, (41.4 g ; 0.255 mol) was charged into the flask via syringe. Carbon dioxide was sparged through the solution for 5 minutes, thereby generating (Me2NCO2)(Me2N)2SiH in situ as set forth by examples in U.S. - A - 4,400,526.
  • the carbon dioxide sparge was stopped and subsequently replaced by an ammonia sparge. After 1 hour at room temperature the starting aminosilane, HSi(NMe2)3, was consumed. The clear water-white liquid was allowed to stir at ambient temperature; after 2 hours the reaction mixture gelled. The reaction flask was refitted for maintaining a vacuum and the solvent was removed by vacuum evaporation (5.32 mbar-4 mmHg) for 8 hours to yield a glassy white solid (20.62 g ). The material was ground to a free flowing white powder and dried again under vacuum (0.133 mbar -0.1 mm Hg) for an additional 8 hours showing no substantial weight loss.
  • Example 8 A reaction apparatus identical to that in Example 8 was charged with dry toluene (60 ml) and the aminosilane, HSi(NMe2)3(49.3 g ; 0.306 mol).
  • the transamination catalyst CH3C6H4SO3H . H2O (0.582 g ; 3.06 mmol) was added as a solid. Immediate gassing was observed due to the reaction of HSi(NMe2)3 with the water of solvation of the catalyst.
  • the reaction mixture was sparged with MeNH2 at room temperature. After 1.5 hours, the aminosilane was consumed.
  • reaction flask was refitted so that the solvent could be removed by vacuum evaporation (0.133 mbar-0.1 mm Hg) and gentle heating to 50°C. Complete removal of the solvent yielded a turbid off white semi-viscous liquid (24.0 g ).
  • Table I above is to illustrate that compounds having an Si-H aminosilane linkage are effectively catalyzed by the method of the invention by catalysts with sources of carbon dioxide (examples 1-5, 8) or by strong organic acids (examples 6, 7 and 9).
  • a 50 ml 3 neck round bottom flask was fitted with a coiled condenser, magnetic stirrer and stirring bar, gas sparging tube, thermometer and fittings for maintaining a dry nitrogen atmosphere.
  • the flask was charged with the aminosilane, Si(NMe2)4, (32.8 g , 160.78 mmol) the solvent toluene (35 ml) and the catalyst, CF3SO3H (0.24 gm, 1.61 mmol) via syringe.
  • the solution was sparged with NH3 for 2 hours at room temperature and then heated to reflux approximately seven hours. Removal of the solvent by vacuum evaporation yielded a white powdery solid (18.0 g ).
  • the white solid (4.50 g ) was fired to 1000°C under a nitrogen atmosphere to yield a dark grey powdery solid (1.80 g) corresponding to a ceramic yield of 40.0% based on weight charges versus weight recovered.
  • Example 12 A reaction apparatus similar to that described in Example 12 was charged with toluene (35 ml ), Si(NMe2)4 (27.3 g ; 132.82 mmol) and CF3SO3H (0.20 g ; 1.3382 mmol) via syringe.
  • the water white solution was sparged with CH3NH2 for 2 hours at room temperature and then heated to reflux for 7 hours. Removal of the solvent by vacuum evaporation yielded a white crystalline solid (14.20 g ).
  • the crystalline tacky solid (4.70 g ) was fired to 1000°C under N2 to yield a black crusta;some solid (2.85 g ) corresponding to a ceramic yield of 60.6% based on weight of material charged vs. weight material recovered.
  • a 500 ml three neck round bottom flask was fitted with a Friedrich condenser, magnetic stirrer and stirring bar, gas sparging tube, thermometer and fittings for maintaining a dry N2 atmosphere.
  • the solution was sparged with CH3NH2 for 2 hours at room temperature.
  • the flask was then charged with HSi(NMe2)3 (41.5 g ; 0.257 mol) and the CH3NH2 was continued for another hour.
  • Class 2 aminosilane compounds are relatively unaffected by the mild organic acids or catalysts which affect Class 1 compounds, and are rather more effectively transaminated using strong organic or inorganic acids.

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Claims (13)

  1. Verfahren zur Herstellung von Silazanpolymeren mit 3 oder mehreren Wiederkehreinheiten der allgemeinen Formel



            ⁅ ((CH₃)₂N)eSi(R)a(R'HN)fHc(NR')g ⁆ ,



    worin R Wasserstoff, eine Vinylgruppe, eine Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Arylgruppe mit 6 bis 12 Kohlenstoffatomen bedeutet,
    a = 0 oder 1, b = 2-4, c = 0-2, d = 0 oder 1, e = 0-2, f = 0-2, g = 1-3 und a+c+e+f+g = 4
    Figure imgb0010
     für die Polymereinheiten ist,
    und R' Wasserstoff oder Methyl bedeutet,
    wobei das Silazanpolymer im wesentlichen frei von Halogenidverunreinigungen ist,
    dadurch gekennzeichnet, dass man halogenfreies Aminosilan der allgemeinen Formel
       (R)a((CH₃)₂N)bHcSi, worin
    R die angegebene Bedeutung hat und a+b+c = 4
    Figure imgb0011
     ist,
    mit einem Amin der allgemeinen Formel
       (CH₃)dNH3-d , wobei d die angegebene Bedeutung hat und das Amin ein Molekulargewicht < 45 hat,
    in Gegenwart eines Säurekatalysators oder des Ammoniumsalzes der Säure transaminiert und anschliessend zur Herstellung des Polymers kondensiert.
  2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass a gleich 0, b gleich 3, c gleich 1 und d gleich 0 oder 1 ist.
  3. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass R gleich CH=CH₂, a gleich 1, b gleich 3, c gleich 0 und d gleich 0 oder 1 ist.
  4. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass R gleich Methyl oder Ethyl, a gleich 1, b gleich 3, c gleich 0 und d gleich 0 oder 1 ist.
  5. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass der Katalysator eine starke organische oder anorganische Säure mit einem pKa-Wert von weniger als 2,2 oder deren Ammoniumsalz ist.
  6. Verfahren gemäss Anspruch 5, dadurch gekennzeichnet, dass die starke organische oder anorganische Säure aus Trifluormethylsulfonsäure, Paratoluolsulfonsäure, Methylsulfonsäure, Schwefelsäure, Salpetersäure, Phosphorsäure und Trifluoressigsäure ausgewählt wird.
  7. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass der Katalysator eine Kohlendioxidquelle, vorzugsweise Kohlendioxid, ein Anmoniumcarbamat und/oder ein Carbamatsilan ist.
  8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Transaminierungsreaktion bei einer Temperatur von 20 bis 200°C ausgeführt wird.
  9. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Transaminierungsreaktion in einem Lösungsmittel, das unter den Reaktionsbedingungen ausgesprochen inert ist, durchgeführt wird.
  10. Verfahren gemäss Anspruch 9, dadurch gekennzeichnet, dass das Lösungsmittel aus Alkanen oder Alkylbenzolen mit 6 bis 20 Kohlenstoffatomen, in denen die Reaktionsprodukte unlöslich sind, oder aus Alkanen oder Alkylbenzolen mit 6 bis 10 Kohlenstoffatomen, in denen die Reaktionsprodukte löslich sind, ausgewählt wird.
  11. Verfahren gemäss Anspruch 10, dadurch gekennzeichnet, dass das Lösungsmittel Toluol oder Xylol ist.
  12. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das Aminosilan ein Gemisch aus Tris(dimethylamino)silan und Vinyltris(dimethylamino)silan ist und entweder NH₃ oder CH₃NH₂ als das Amin eingesetzt wird.
  13. Verfahren gemäss einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass es zusätzlich eine Pyrolyse, um Siliciumnitrid zu geben, umfasst.
EP87104014A 1986-03-19 1987-03-18 Verfahren zur Herstellung von Polysilazanen und Silicium-Nitriden Expired - Lifetime EP0238078B1 (de)

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AT87104014T ATE87640T1 (de) 1986-03-19 1987-03-18 Verfahren zur herstellung von polysilazanen und silicium-nitriden.

Applications Claiming Priority (2)

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US841545 1986-03-19
US06/841,545 US4675424A (en) 1986-03-19 1986-03-19 Method for making polysilazanes

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EP0238078A2 EP0238078A2 (de) 1987-09-23
EP0238078A3 EP0238078A3 (en) 1990-04-11
EP0238078B1 true EP0238078B1 (de) 1993-03-31

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US (1) US4675424A (de)
EP (1) EP0238078B1 (de)
JP (1) JPS62225534A (de)
AT (1) ATE87640T1 (de)
CA (1) CA1256632A (de)
DE (1) DE3785065T2 (de)

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FR2590580B1 (fr) * 1985-11-28 1988-05-13 Rhone Poulenc Spec Chim Procede de traitement catalytique d'un polysilazane comportant en moyenne au moins deux groupes hydrocarbone a insaturation aliphatique par molecule
US5120686A (en) * 1985-12-20 1992-06-09 The Dexter Corporation Method of preparing a polysilazane
JPH0618885B2 (ja) * 1986-02-12 1994-03-16 東燃株式会社 ポリシロキサザンおよびその製法
US5166104A (en) * 1986-02-12 1992-11-24 Toa Nenryo Kogyo Kabushiki Kaisha Polysiloxazanes, silicon oxynitride fibers and processes for producing same
JPS62290730A (ja) * 1986-06-10 1987-12-17 Shin Etsu Chem Co Ltd 有機シラザン重合体の製造方法
US4916200A (en) * 1987-06-08 1990-04-10 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
US4861569A (en) * 1987-08-13 1989-08-29 Petroleum Energy Center Reformed, inorganic polysilazane and method of producing same
US4895889A (en) * 1988-05-12 1990-01-23 Ethyl Corporation Preceramic compositions
DE3832933A1 (de) * 1988-09-28 1990-03-29 Wacker Chemie Gmbh Verfahren zur herstellung von polysilazanen
US4929742A (en) * 1988-11-28 1990-05-29 Dow Corning Corporation Silane modified polysilacyclobutasilazanes
US5189132A (en) * 1988-12-03 1993-02-23 Hoechst Aktiengesellschaft Polymeric hydridochlorosilazanes, process for their preparation, ceramic materials containing silicon nitride which can be manufactured therefrom, and their manufacture
US5097364A (en) * 1988-12-12 1992-03-17 Mitsubishi Denki Kabushiki Kaisha Magnetic recording and reproducing apparatus and method of recording and reproducing
US4929704A (en) * 1988-12-20 1990-05-29 Hercules Incorporated Isocyanate- and isothiocyanate-modified polysilazane ceramic precursors
FR2642431A1 (fr) * 1989-01-30 1990-08-03 Rhone Poulenc Chimie Procede de reticulation de polysilazanes
US5198519A (en) * 1991-04-25 1993-03-30 The Standard Oil Company Silazane polymers and method of making same
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US5612414A (en) * 1993-11-05 1997-03-18 Lanxide Technology Company, Lp Organic/inorganic polymers
US9382269B2 (en) 2013-09-27 2016-07-05 Voltaix, Llc Halogen free syntheses of aminosilanes by catalytic dehydrogenative coupling
US9777025B2 (en) 2015-03-30 2017-10-03 L'Air Liquide, Société pour l'Etude et l'Exploitation des Procédés Georges Claude Si-containing film forming precursors and methods of using the same
US11124876B2 (en) 2015-03-30 2021-09-21 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Si-containing film forming precursors and methods of using the same
US9593210B1 (en) * 2015-06-03 2017-03-14 General Electric Company Methods of preparing polysilazane resin with low halogen content
CN108431013B (zh) * 2015-12-18 2021-03-16 美国陶氏有机硅公司 二硅烷基胺和聚硅烷基胺的合成
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Also Published As

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EP0238078A2 (de) 1987-09-23
ATE87640T1 (de) 1993-04-15
EP0238078A3 (en) 1990-04-11
DE3785065D1 (de) 1993-05-06
JPS62225534A (ja) 1987-10-03
US4675424A (en) 1987-06-23
JPH0460492B2 (de) 1992-09-28
CA1256632A (en) 1989-06-27
DE3785065T2 (de) 1993-07-08

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